Yuanzhe Li*, Sebastian O. Danielache*, Yoshiaki Endo, Shinkoh Nanbu and Yuichiro Ueno,
{"title":"32S、33S、34S 和 36S 二氧化硫 B~1B1-X~1A1 吸收带的高分辨率紫外吸收截面测量结果","authors":"Yuanzhe Li*, Sebastian O. Danielache*, Yoshiaki Endo, Shinkoh Nanbu and Yuichiro Ueno, ","doi":"10.1021/acsearthspacechem.4c0014710.1021/acsearthspacechem.4c00147","DOIUrl":null,"url":null,"abstract":"<p >We report newly measured high-resolution and high-precision ultraviolet absorption cross-sections of <sup>32</sup>SO<sub>2</sub>, <sup>33</sup>SO<sub>2</sub>, <sup>34</sup>SO<sub>2</sub>, and <sup>36</sup>SO<sub>2</sub> for the <i></i><math><msup><mover><mi>B</mi><mo>~</mo></mover><mn>1</mn></msup><msub><mi>B</mi><mn>1</mn></msub><mo>−</mo><msup><mover><mi>X</mi><mo>~</mo></mover><mn>1</mn></msup><msub><mi>A</mi><mn>1</mn></msub></math> band over the wavelength range of 240 to 320 nm at a resolution of 0.4 cm<sup>–1</sup>. The resolution was improved 20 times compared to that in a previous study. A least absolute deviation linear regression method was applied to calculate cross-sections and derived spectral errors from a set of measurements recorded at a wide range of pressures to ensure the optimal signal-to-noise ratio at all wavelengths. Based on this analysis, error bars on the measured cross-sections ranged between 3 and 10%. The overall features of measured cross-sections, such as peak positions of the isotopologues, are consistent with previous studies. We provide improved spectral data for studying sulfur mass-independent fraction (S-MIF) signatures during SO<sub>2</sub> photoexcitation. Our spectral measurements predict that SO<sub>2</sub> photoexcitation produces S-MIF enrichment factors <sup>33</sup><i>E</i> = – 0.9 ± 0.2‰ and <sup>36</sup><i>E</i> = – 3.8 ± 0.4‰ (where <sup>33</sup><i>E</i> and <sup>36</sup><i>E</i> are 1000 × [ln(<sup>33</sup><i>J</i>/<sup>32</sup><i>J</i>) – 0.515 ln(<sup>34</sup><i>J</i>/<sup>32</sup><i>J</i>)] ‰ and 1000 × [ln(<sup>36</sup><i>J</i>/<sup>32</sup><i>J</i>) – 1.90 ln(<sup>34</sup><i>J</i>/<sup>32</sup><i>J</i>] ‰, and <sup>3<i>x</i></sup><i>J</i> is the <sup>3<i>x</i></sup>SO<sub>2</sub> photoexcitation rate constant). Based on this new result, we found that calculated SO<sub>2</sub> photoexcitation isotope effects are smaller than previously thought and generally do not match photoexcitation experimental observations supporting the hypothesis of an intersystem crossing origin of MIF on those experiments.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00147","citationCount":"0","resultStr":"{\"title\":\"High-Resolution UV Absorption Cross-Section Measurements of 32S, 33S, 34S, and 36S Sulfur Dioxide for the B~1B1−X~1A1 Absorption Band\",\"authors\":\"Yuanzhe Li*, Sebastian O. Danielache*, Yoshiaki Endo, Shinkoh Nanbu and Yuichiro Ueno, \",\"doi\":\"10.1021/acsearthspacechem.4c0014710.1021/acsearthspacechem.4c00147\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We report newly measured high-resolution and high-precision ultraviolet absorption cross-sections of <sup>32</sup>SO<sub>2</sub>, <sup>33</sup>SO<sub>2</sub>, <sup>34</sup>SO<sub>2</sub>, and <sup>36</sup>SO<sub>2</sub> for the <i></i><math><msup><mover><mi>B</mi><mo>~</mo></mover><mn>1</mn></msup><msub><mi>B</mi><mn>1</mn></msub><mo>−</mo><msup><mover><mi>X</mi><mo>~</mo></mover><mn>1</mn></msup><msub><mi>A</mi><mn>1</mn></msub></math> band over the wavelength range of 240 to 320 nm at a resolution of 0.4 cm<sup>–1</sup>. The resolution was improved 20 times compared to that in a previous study. A least absolute deviation linear regression method was applied to calculate cross-sections and derived spectral errors from a set of measurements recorded at a wide range of pressures to ensure the optimal signal-to-noise ratio at all wavelengths. Based on this analysis, error bars on the measured cross-sections ranged between 3 and 10%. The overall features of measured cross-sections, such as peak positions of the isotopologues, are consistent with previous studies. We provide improved spectral data for studying sulfur mass-independent fraction (S-MIF) signatures during SO<sub>2</sub> photoexcitation. Our spectral measurements predict that SO<sub>2</sub> photoexcitation produces S-MIF enrichment factors <sup>33</sup><i>E</i> = – 0.9 ± 0.2‰ and <sup>36</sup><i>E</i> = – 3.8 ± 0.4‰ (where <sup>33</sup><i>E</i> and <sup>36</sup><i>E</i> are 1000 × [ln(<sup>33</sup><i>J</i>/<sup>32</sup><i>J</i>) – 0.515 ln(<sup>34</sup><i>J</i>/<sup>32</sup><i>J</i>)] ‰ and 1000 × [ln(<sup>36</sup><i>J</i>/<sup>32</sup><i>J</i>) – 1.90 ln(<sup>34</sup><i>J</i>/<sup>32</sup><i>J</i>] ‰, and <sup>3<i>x</i></sup><i>J</i> is the <sup>3<i>x</i></sup>SO<sub>2</sub> photoexcitation rate constant). Based on this new result, we found that calculated SO<sub>2</sub> photoexcitation isotope effects are smaller than previously thought and generally do not match photoexcitation experimental observations supporting the hypothesis of an intersystem crossing origin of MIF on those experiments.</p>\",\"PeriodicalId\":15,\"journal\":{\"name\":\"ACS Earth and Space Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00147\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Earth and Space Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsearthspacechem.4c00147\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Earth and Space Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsearthspacechem.4c00147","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
High-Resolution UV Absorption Cross-Section Measurements of 32S, 33S, 34S, and 36S Sulfur Dioxide for the B~1B1−X~1A1 Absorption Band
We report newly measured high-resolution and high-precision ultraviolet absorption cross-sections of 32SO2, 33SO2, 34SO2, and 36SO2 for the band over the wavelength range of 240 to 320 nm at a resolution of 0.4 cm–1. The resolution was improved 20 times compared to that in a previous study. A least absolute deviation linear regression method was applied to calculate cross-sections and derived spectral errors from a set of measurements recorded at a wide range of pressures to ensure the optimal signal-to-noise ratio at all wavelengths. Based on this analysis, error bars on the measured cross-sections ranged between 3 and 10%. The overall features of measured cross-sections, such as peak positions of the isotopologues, are consistent with previous studies. We provide improved spectral data for studying sulfur mass-independent fraction (S-MIF) signatures during SO2 photoexcitation. Our spectral measurements predict that SO2 photoexcitation produces S-MIF enrichment factors 33E = – 0.9 ± 0.2‰ and 36E = – 3.8 ± 0.4‰ (where 33E and 36E are 1000 × [ln(33J/32J) – 0.515 ln(34J/32J)] ‰ and 1000 × [ln(36J/32J) – 1.90 ln(34J/32J] ‰, and 3xJ is the 3xSO2 photoexcitation rate constant). Based on this new result, we found that calculated SO2 photoexcitation isotope effects are smaller than previously thought and generally do not match photoexcitation experimental observations supporting the hypothesis of an intersystem crossing origin of MIF on those experiments.
期刊介绍:
The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.